Molecular sieve composition (EMM-10-P), its method of making, and use for hydrocarbon conversions

ABSTRACT

This invention relates to a crystalline molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern including d-spacing maxima at 13.18±0.25 and 12.33±0.23 Angstroms, wherein the peak intensity of the d-spacing maximum at 13.18±0.25 Angstroms is at least as great as 90% of the peak intensity of the d-spacing maximum at 12.33±0.23 Angstroms. This invention also relates to a method of making thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/004,991, filed Jan. 12, 2011, U.S. patent application Ser. No.11/823,129, filed Jun. 27, 2007, now U.S. Pat. No. 7,959,899, whichclaims benefit of U.S. Provisional Patent Application No. 60/834,030,filed Jul. 28, 2006, U.S. Provisional Patent Application No. 60/834,001,filed Jul. 28, 2006, U.S. Provisional Patent Application No. 60/834,031,filed Jul. 28, 2006, and U.S. Provisional Patent Application No.60/926,204, filed Apr. 25, 2007, the references of which are hereinincorporated by reference in their entireties.

FIELD

This invention relates to a novel molecular sieve composition(EMM-10-P), a method of making thereof and the use thereof forhydrocarbon conversions. In particular, this invention relates to anovel MCM-22 family molecular sieve composition, a method of makingthereof and the use thereof for hydrocarbon conversions.

BACKGROUND OF THIS DISCLOSURE

Molecular sieve materials, both natural and synthetic, have beendemonstrated in the past to have catalytic properties for various typesof hydrocarbon conversion. Certain molecular sieves, zeolites, AlPOs,mesoporous materials, are ordered, porous crystalline materials having adefinite crystalline structure as determined by X-ray diffraction (XRD).Within the crystalline molecular sieve material there are a large numberof cavities which may be interconnected by a number of channels orpores. These cavities and pores are uniform in size within a specificmolecular sieve material. Because the dimensions of these pores are suchas to accept for adsorption molecules of certain dimensions whilerejecting those of larger dimensions, these materials have come to beknown as “molecular sieves” and are utilized in a variety of industrialprocesses.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline silicates. Thesesilicates can be described as rigid three-dimensional framework of SiO₄and Periodic Table Group 13 element oxide (e.g., AlO₄). The tetrahedraare cross-linked by the sharing of oxygen atoms whereby the ratio of thetotal Group 13 element (e.g., aluminum) and silicon atoms to oxygenatoms is 1:2. The electrovalence of the tetrahedra containing the Group13 element (e.g., aluminum) is balanced by the inclusion in the crystalof a cation, for example a proton, an alkali metal or an alkaline earthmetal cation. This can be expressed wherein the ratio of the Group 13element (e.g., aluminum) to the number of various cations, such as H⁺,Ca²⁻/2, Sr²⁺/2, Na⁺, K⁺, or Li⁺, is equal to unity.

Molecular sieves that find application in catalysis include any of thenaturally occurring or synthetic crystalline molecular sieves. Examplesof these zeolites include large pore zeolites, intermediate pore sizezeolites, and small pore zeolites. These zeolites and their isotypes aredescribed in “Atlas of Zeolite Framework Types”, eds. W. H. Meier, D. H.Olson and Ch. Baerlocher, Elsevier, Fifth Edition, 2001, which is herebyincorporated by reference. A large pore zeolite generally has a poresize of at least about 7 Å and includes LTL, VFI, MAZ, FAU, OFF, *BEA,and MOR framework type zeolites (IUPAC Commission of ZeoliteNomenclature). Examples of large pore zeolites include mazzite,offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and Beta. Anintermediate pore size zeolite generally has a pore size from about 5 Åto less than about 7 Å and includes, for example, MFI, MEL, EUO, MTT,MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites (IUPACCommission of Zeolite Nomenclature). Examples of intermediate pore sizezeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, andsilicalite 2. A small pore size zeolite has a pore size from about 3 Åto less than about 5.0 Å and includes, for example, CHA, ERI, KFI, LEV,SOD, and LTA framework type zeolites (IUPAC Commission of ZeoliteNomenclature). Examples of small pore zeolites include ZK-4, ZSM-2,SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A,chabazite, zeolite T, gmelinite, ALPO-17, and clinoptilolite.

U.S. Pat. No. 4,439,409 refers to a crystalline molecular sievecomposition of matter named PSH-3 and its synthesis from a hydrothermalreaction mixture containing hexamethyleneimine, an organic compoundwhich acts as directing agent for synthesis of the MCM-56 (U.S. Pat. No.5,362,697). Hexamethyleneimine is also taught for use in synthesis ofcrystalline molecular sieves MCM-22 (U.S. Pat. No. 4,954,325) and MCM-49(U.S. Pat. No. 5,236,575). A molecular sieve composition of matterreferred to as zeolite SSZ-25 (U.S. Pat. No. 4,826,667) is synthesizedfrom a hydrothermal reaction mixture containing an adamantane quaternaryammonium ion. U.S. Pat. No. 6,077,498 refers to a crystalline molecularsieve composition of matter named ITQ-1 and its synthesis from ahydrothermal reaction mixture containing one or a plurality of organicadditives.

The term “MCM-22 family material” (or “material of the MCM-22 family” or“molecular sieve of the MCM-22 family”), as used herein, includes:

-   (i) molecular sieves made from a common first degree crystalline    building block “unit cell having the MWW framework topology”. A unit    cell is a spatial arrangement of atoms which is tiled in    three-dimensional space to describe the crystal as described in the    “Atlas of Zeolite Framework Types”, Fifth edition, 2001, the entire    content of which is incorporated as reference;-   (ii) molecular sieves made from a common second degree building    block, a 2-dimensional tiling of such MWW framework type unit cells,    forming a “monolayer of one unit cell thickness”, preferably one    c-unit cell thickness;-   (iii) molecular sieves made from common second degree building    blocks, “layers of one or more than one unit cell thickness”,    wherein the layer of more than one unit cell thickness is made from    stacking, packing, or binding at least two monolayers of one unit    cell thick of unit cells having the MWW framework topology. The    stacking of such second degree building blocks can be in a regular    fashion, an irregular fashion, a random fashion, or any combination    thereof; or-   (iv) molecular sieves made by any regular or random 2-dimensional or    3-dimensional combination of unit cells having the MWW framework    topology.

The MCM-22 family materials are characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 3.57±0.07and 3.42±0.07 Angstroms (either calcined or as-synthesized). The MCM-22family materials may also be characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized).The X-ray diffraction data used to characterize the molecular sieve areobtained by standard techniques using the K-alpha doublet of copper asthe incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials belong to the MCM-22 family include MCM-22 (described in U.S.Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409),SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described inEuropean Patent No. 0293032), ITQ-1 (described in U.S. Pat. No.6,077,498), ITQ-2 (described in International Patent Publication No.WO97/17290), ITQ-30 (described in International Patent Publication No.WO2005118476), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49(described in U.S. Pat. No. 5,236,575) and MCM-56 (described in U.S.Pat. No. 5,362,697). The entire contents of the patents are incorporatedherein by reference.

It is to be appreciated the MCM-22 family molecular sieves describedabove are distinguished from conventional large pore zeolite alkylationcatalysts, such as mordenite, in that the MCM-22 materials have 12-ringsurface pockets which do not communicate with the 10-ring internal poresystem of the molecular sieve.

The zeolitic materials designated by the IZA-SC as being of the MWWtopology are multi-layered materials which have two pore systems arisingfrom the presence of both 10 and 12 membered rings. The Atlas of ZeoliteFramework Types classes five differently named materials as having thissame topology: MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

The MCM-22 family molecular sieves have been found to be useful in avariety of hydrocarbon conversion processes. Examples of MCM-22 familymolecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, andERB-1. Such molecular sieves are useful for alkylation of aromaticcompounds. For example, U.S. Pat. No. 6,936,744 discloses a process forproducing a monoalkylated aromatic compound, particularly cumene,comprising the step of contacting a polyalkylated aromatic compound withan alkylatable aromatic compound under at least partial liquid phaseconditions and in the presence of a transalkylation catalyst to producethe monoalkylated aromatic compound, wherein the transalkylationcatalyst comprises a mixture of at least two different crystallinemolecular sieves, wherein each of the molecular sieves is selected fromzeolite beta, zeolite Y, mordenite and a material having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms.

Chem. Lett. Vol. 32, No. 6, page 542-543 (2003) by S. H. Lee, C. H.Shin, and S. B Hong and Microporous and Mesoporous Materials, Vol. 68,page 97-104 (2004) by S. H. Lee, C. H. Shin, D. K. Yang, S. D. Ahn, I.S. Nam and S. B Hong reported a MCM-22 molecular sieve synthesized bycrystallizing hydrothermal reaction mixtures prepared from water,Me₆-diquat-5 dibromide, Ludox HS-40, aluminum nitrate non-hydrate, and50 wt % sodium hydroxide solution. The mixtures had a molar compositionas shown in Table I. The mixtures were crystallized undercrystallization conditions (as shown in Table I) and characterized aspure phase MCM-22 with a crystal size of about 0.5×0.05 μm (micro platesmorphology).

TABLE I Microporous and Chem. Lett. Vol. 32, Mesoporous Materials, No.6, page 542-543 Vol. 68, page 97-104 (2003) (2004) Molar composition ofthe mixture SiO₂/Al₂O₃ 60 30 60 H₂O/SiO₂ 40 40 40 OH⁻/SiO₂* 0.63 0.4 0.5OH⁻/SiO₂** 0.73 0.6 0.6 Na⁺/SiO₂ 0.73 0.6 0.6 R/SiO₂ 0.15 0.1 0.1Crystallization conditions Temperature (° C.) 160 Stirring speed (RPM)100 Time (hr) 168 Product Characterization XRD Result Pure Phase MCM-22SiO₂/Al₂O₃ (molar ratio) 38 BET area (m²/g) 438 Crystal size 0.5 × 0.05μm Morphology Platelet Platelet *The OH⁻/SiO₂ of this row is calculatedwith correction of aluminum source, wherein Al(NO₃)₃ was used in bothpapers. **The OH⁻/SiO₂ of this row is calculated without correction ofaluminum source.

It is known that crystal morphology, size and aggregation/agglomerationcan affect catalyst behavior, especially regarding catalyst activity andstability. There is, therefore, a need for novel crystalline molecularsieve compositions and method of making such novel crystalline molecularsieve compositions, especially molecular sieves of different morphology.

SUMMARY OF THIS DISCLOSURE

This disclosure relates to a crystalline molecular sieve, in itsas-synthesized form, identified as EMM-10-P. This disclosure alsorelates to a method of making EMM-10-P. In some preferred embodiments,the EMM-10-P is an MCM-22 family molecular sieve.

In some embodiments, this disclosure relates to a crystalline molecularsieve having, in its as-synthesized form, an X-ray diffraction patternincluding d-spacing maxima at 13.18±0.25 and 12.33±0.23 Angstroms,wherein the peak intensity of the d-spacing maximum at 13.18±0.25Angstroms is at least as great as 90% of the peak intensity of thed-spacing maximum at 12.33±0.23 Angstroms.

In additional embodiments of this disclosure, the X-ray diffractionpattern of the crystalline molecular sieve further includes two XRDdistinguishable peaks with d-spacing maxima at 11.06±0.18 and 9.25±0.13Angstroms, wherein the peak intensity of the d-spacing maximum at11.06±0.18 Angstroms is at least as great as the peak intensity of thed-spacing maximum at 9.25±0.13 Angstroms. Additionally, the peaks withd-spacing maxima at 11.06±0.18 and 9.25±0.13 Angstroms may benon-discrete peaks.

In yet more embodiments, this disclosure relates to a crystalline MCM-22family molecular sieve that has a total surface area of greater than 450m²/g as measured by the N₂ BET method. The crystalline MCM-22 familymolecular sieve preferably has a ratio of the external surface area overthe total surface area of less than 0.15 after conversion into H-form byexchange with ammonium nitrate and calcination, wherein the externalsurface area is determined from a t-plot of the N₂ BET.

In yet some additional embodiments, this disclosure relates to acrystalline molecular sieve that has a morphology of tabular habit,wherein at least 50 wt % of the crystalline molecular sieve have acrystal diameter greater than 1 μm as measured by the SEM, preferablygreater than 2 μm as measured by the SEM.

In some aspects, the crystalline molecular sieve has a morphology oftabular habit, wherein at least 50 wt % of the crystalline molecularsieve have a crystal thickness of about 0.025 μm as measured by the SEM.

In one aspect, the crystalline molecular sieve of this disclosure is anMCM-22 family molecular sieve.

In some embodiments, this disclosure relates to a method of making acrystalline molecular sieve, the method comprising the steps of:

-   -   (a) providing a mixture comprising at least one source of at        least one tetravalent element (Y), at least one source of at        least one alkali or alkali earth metal element, at least one        directing-agent (R), water, and optionally at least one source        of at least one trivalent element (X), said mixture having the        following molar ratio:        -   Y:X₂=10 to infinity, preferably 10 to 10000, more preferably            from 10 to 55;        -   H₂O:Y=1 to 10000, preferably 1 to 5000, more preferably from            5 to 35;        -   OH⁻:Y without trivalent element source correction=0.001 to            0.59, and/or        -   OH⁻:Y (with trivalent element source correction)=0.001 to            0.39        -   M⁺:Y=0.001 to 2, preferably from 0.1 to 1;        -   R:Y=0.001 to 2, preferably from 0.1 to 1;        -   wherein M is an alkali metal and R is at least one            N,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium salt            (Me₆-diquat-5 salt(s)), preferably R is selected from the            group consisting of Me₆-diquat-5 dibromide, Me₆-diquat-5            dichloride, Me₆-diquat-5 difluoride, Me₆-diquat-5 diiodide,            Me₆-diquat-5 dihydroxide, Me₆-diquat-5 sulfate, Me₆-diquat-5            dinitrate, Me₆-diquat-5 hydroxide bromide, Me₆-diquat-5            hydroxide chloride, Me₆-diquat-5 hydroxide fluoride,            Me₆-diquat-5 hydroxide iodide, Me₆-diquat-5 hydroxide            nitrate, Me₆-diquat-5 fluoride bromide, Me₆-diquat-5            fluoride chloride, Me₆-diquat-5 fluoride iodide,            Me₆-diquat-5 fluoride nitrate, Me₆-diquat-5 chloride            bromide, Me₆-diquat-5 chloride iodide, Me₆-diquat-5 chloride            nitrate, Me₆-diquat-5 iodide bromide, Me₆-diquat-5 bromide            nitrate, and any mixtures thereof, more preferably R is            selected from the group consisting of Me₆-diquat-5            dibromide, Me₆-diquat-5 dichloride, Me₆-diquat-5 difluoride,            Me₆-diquat-5 diiodide, Me₆-diquat-5 dihydroxide,            Me₆-diquat-5 sulfate, Me₆-diquat-5 dinitrate, and any            mixtures thereof, most preferably R is Me₆-diquat-5            dibromide; and    -   (b) submitting the mixture at crystallization conditions to form        a product comprising the desired crystalline molecular sieve,        wherein the crystallization conditions comprise a temperature in        the range of from 100° C. to 200° C., preferably from about 140        to about 180 C; and a crystallization time from about 1 hour to        400 hours, preferably from about 1 to 200 hours, optionally a        stirring speed in the range of from 0 to 1000 RPM, preferably        from 0 to 400 RPM.

In additional embodiments, this disclosure relates to a method ofmanufacturing a crystalline molecular sieve, the method comprising thesteps of:

-   -   (a) providing a mixture comprising at least one source of at        least one tetravalent element (Y), at least one source of at        least one alkali or alkali earth metal element, at least one        directing-agent (R), water, and optionally at least one source        of at least one trivalent element (X), said mixture having the        following molar ratio:        -   Y:X₂=10 to infinity, preferably 10 to 10000, more preferably            from about 10 to 55;        -   H₂O:Y=1 to 10000, preferably 1 to 5000, more preferably from            5 to 35;        -   OH⁻:Y without trivalent element source correction=0.74 to 2            and/or OH⁻:Y with trivalent element source correction=0.64            to 2        -   M⁺:Y=0.001 to 2, preferably from 0.1 to 1;        -   R:Y=0.001 to 2, preferably from 0.1 to 1;        -   wherein M is an alkali metal and R is at least one            N,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium salt            (Me₆-diquat-5 salt(s)), preferably R is selected from the            group consisting of Me₆-diquat-5 dibromide, Me₆-diquat-5            dichloride, Me₆-diquat-5 difluoride, Me₆-diquat-5 diiodide,            Me₆-diquat-5 dihydroxide, Me₆-diquat-5 sulfate, Me₆-diquat-5            dinitrate, Me₆-diquat-5 hydroxide bromide, Me₆-diquat-5            hydroxide chloride, Me₆-diquat-5 hydroxide fluoride,            Me₆-diquat-5 hydroxide iodide, Me₆-diquat-5 hydroxide            nitrate, Me₆-diquat-5 fluoride bromide, Me₆-diquat-5            fluoride chloride, Me₆-diquat-5 fluoride iodide,            Me₆-diquat-5 fluoride nitrate, Me₆-diquat-5 chloride            bromide, Me₆-diquat-5 chloride iodide, Me₆-diquat-5 chloride            nitrate, Me₆-diquat-5 iodide bromide, Me₆-diquat-5 bromide            nitrate, and any mixtures thereof, more preferably R is            selected from the group consisting of Me₆-diquat-5            dibromide, Me₆-diquat-5 dichloride, Me₆-diquat-5 difluoride,            Me₆-diquat-5 diiodide, Me₆-diquat-5 dihydroxide,            Me₆-diquat-5 sulfate, Me₆-diquat-5 dinitrate, and any            mixtures thereof, most preferably R is Me₆-diquat-5            dibromide;    -   (b) submitting the mixture at crystallization conditions to form        a product comprising the desired crystalline molecular sieve,        wherein the crystallization conditions comprise a temperature in        the range of from 100° C. to 200° C., preferably from about 140        to about 180 C; and a crystallization time from about 1 hour to        400 hours, preferably from about 1 to 200 hours, optionally a        stirring speed in the range of from 0 to 1000 RPM, preferably        from 0 to 400 RPM; and    -   (c) recovering the crystalline molecular sieve.

In yet additional embodiments, this disclosure relates to a method ofmanufacturing a crystalline molecular sieve, the method comprising thesteps of:

-   -   (a) providing a mixture comprising at least one source of at        least one tetravalent element (Y), at least one source of at        least one alkali or alkali earth metal element, at least one        directing-agent (R), water, and optionally at least one source        of at least one trivalent element (X), said mixture having the        following molar ratio:        -   Y:X₂=10 to infinity, preferably 10 to 10000, more preferably            from about 10 to 55;        -   H₂O:Y=1 to 10000, preferably 1 to 5000, more preferably from            5 to 35;        -   OH⁻:Y without trivalent element source correction=0.61 to            0.72 and/or OH⁻:Y with trivalent element source            correction=0.41 to 0.49 or 0.51 to 0.62        -   M⁺:Y=0.001 to 2, preferably from 0.1 to 1;        -   R:Y=0.001 to 2, preferably from 0.1 to 1;        -   wherein M is an alkali metal and R is at least one            N,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium salt            (Me₆-diquat-5 salt(s)), preferably R is selected from the            group consisting of Me₆-diquat-5 dibromide, Me₆-diquat-5            dichloride, Me₆-diquat-5 difluoride, Me₆-diquat-5 diiodide,            Me₆-diquat-5 dihydroxide, Me₆-diquat-5 sulfate, Me₆-diquat-5            dinitrate, Me₆-diquat-5 hydroxide bromide, Me₆-diquat-5            hydroxide chloride, Me₆-diquat-5 hydroxide fluoride,            Me₆-diquat-5 hydroxide iodide, Me₆-diquat-5 hydroxide            nitrate, Me₆-diquat-5 fluoride bromide, Me₆-diquat-5            fluoride chloride, Me₆-diquat-5 fluoride iodide,            Me₆-diquat-5 fluoride nitrate, Me₆-diquat-5 chloride            bromide, Me₆-diquat-5 chloride iodide, Me₆-diquat-5 chloride            nitrate, Me₆-diquat-5 iodide bromide, Me₆-diquat-5 bromide            nitrate, and any mixtures thereof, more preferably R is            selected from the group consisting of Me₆-diquat-5            dibromide, Me₆-diquat-5 dichloride, Me₆-diquat-5 difluoride,            Me₆-diquat-5 diiodide, Me₆-diquat-5 dihydroxide,            Me₆-diquat-5 sulfate, Me₆-diquat-5 dinitrate, and any            mixtures thereof, most preferably R is Me₆-diquat-5            dibromide;    -   (b) submitting the mixture at crystallization conditions to form        a product comprising the desired crystalline molecular sieve,        wherein the crystallization conditions comprise a temperature in        the range of from 100° C. to 200° C., preferably from about 140        to about 180 C; and a crystallization time from about 1 hour to        400 hours, preferably from about 1 to 200 hours, optionally a        stirring speed in the range of from 0 to 1000 RPM, preferably        from 0 to 400 RPM; and    -   (c) recovering the crystalline molecular sieve.

In further additional embodiments, this disclosure relates to a methodof manufacturing a crystalline molecular sieve, the method comprisingthe steps of:

-   -   (a) providing a mixture comprising at least one source of at        least one tetravalent element (Y), at least one source of at        least one alkali or alkali earth metal element, at least one        directing-agent (R), water, and optionally at least one source        of at least one trivalent element (X), said mixture having the        following molar ratio:        -   Y:X₂=10 to infinity, preferably 10 to 10000, more preferably            from 10 to 55;        -   H₂O:Y=1 to 35, preferably from 5 to 35;        -   OH⁻:Y=0.001 to 2, preferably from 0.01 to 0.5;        -   M⁺:Y=0.001 to 2, preferably from 0.1 to 1;        -   R:Y=0.001 to 2, preferably from 0.1 to 1;        -   wherein M is an alkali metal and R is at least one            N,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium salt            (Me₆-diquat-5 salt(s)), preferably R is selected from the            group consisting of Me₆-diquat-5 dibromide, Me₆-diquat-5            dichloride, Me₆-diquat-5 difluoride, Me₆-diquat-5 diiodide,            Me₆-diquat-5 dihydroxide, Me₆-diquat-5 sulfate, Me₆-diquat-5            dinitrate, Me₆-diquat-5 hydroxide bromide, Me₆-diquat-5            hydroxide chloride, Me₆-diquat-5 hydroxide fluoride,            Me₆-diquat-5 hydroxide iodide, Me₆-diquat-5 hydroxide            nitrate, Me₆-diquat-5 fluoride bromide, Me₆-diquat-5            fluoride chloride, Me₆-diquat-5 fluoride iodide,            Me₆-diquat-5 fluoride nitrate, Me₆-diquat-5 chloride            bromide, Me₆-diquat-5 chloride iodide, Me₆-diquat-5 chloride            nitrate, Me₆-diquat-5 iodide bromide, Me₆-diquat-5 bromide            nitrate, and any mixtures thereof, more preferably R is            selected from the group consisting of Me₆-diquat-5            dibromide, Me₆-diquat-5 dichloride, Me₆-diquat-5 difluoride,            Me₆-diquat-5 diiodide, Me₆-diquat-5 dihydroxide,            Me₆-diquat-5 sulfate, Me₆-diquat-5 dinitrate, and any            mixtures thereof, most preferably R is Me₆-diquat-5            dibromide, wherein said OH⁻:Y is calculated with or without            trivalent element source correction;    -   (b) submitting the mixture at crystallization conditions to form        a product comprising the desired crystalline molecular sieve,        wherein the crystallization conditions comprise a temperature in        the range of from 100° C. to 200° C., preferably from about 140        to about 180 C; and a crystallization time from about 1 hour to        400 hours, preferably from about 1 to 200 hours, optionally a        stirring speed in the range of from 0 to 1000 RPM, preferably        from 0 to 400 RPM; and    -   (c) recovering the crystalline molecular sieve.

In some embodiments, this disclosure relates to a method ofmanufacturing the crystalline molecular sieve of this disclosure, themethod comprising the steps of:

-   -   (a) combining at least one silicon source, at least one source        of at least one alkali or alkali earth metal element, at least        one directing-agent (R), water, and optionally at least one        aluminum source, to form a mixture having the following mole        composition:        -   Si:Al₂=10 to infinity; preferably 10 to 10000        -   H₂O:Si=1 to 10000; preferably 1 to 5000        -   OH⁻:Si without trivalent element source correction=0.001 to            0.59, and/or        -   OH⁻:Si (with trivalent element source correction)=0.001 to            0.39        -   M⁺:Si=0.001 to 2        -   R:Si=0.001 to 0.34        -   wherein M is an alkali metal and R is at least one            N,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium salt;    -   (b) treating the mixture at crystallization conditions to form a        product comprising the desired crystalline molecular sieve,        wherein the crystallization conditions comprise a temperature in        the range of from 100° C. to 200° C., and a crystallization time        from about 1 hour to 200 hours; and    -   (c) recovering the molecular sieve.

In some aspects, the H2O:Si molar ratio is in the range of from 5 to 35.

Additionally, this disclosure relates to a process for hydrocarbonconversion, comprising the step of:

-   -   (a) contacting a hydrocarbon feedstock with the crystalline        molecular sieve of this disclosure or manufactured by the method        of this disclosure, under conversion conditions to form a        conversion product.

These and other facets of the present invention shall become apparentfrom the following detailed description, Figures, and appended claims.

DESCRIPTION OF THE FIGURES

FIG. 1 shows the X-ray diffraction patterns of the as-synthesized MCM-22family molecular sieve products of Example A.

FIG. 2 shows the SEM image of the as-synthesized MCM-22 family molecularsieve product of Example A.

FIG. 3 shows the X-ray diffraction patterns of the as-synthesized MCM-22family molecular sieve products of Example 1.

FIG. 4 shows the SEM image of the as-synthesized MCM-22 family molecularsieve product of Example 1.

FIG. 5 shows the X-ray diffraction patterns of the as-synthesized MCM-22family molecular sieve products of Example 2.

FIG. 6 shows the SEM image of the as-synthesized MCM-22 family molecularsieve product of Example 2.

FIG. 7 shows the X-ray diffraction patterns of the as-synthesized (top)and the ammonium exchanged and/or calcined MCM-22 family molecular sieveproduct(s) (bottom) of Example 4.

DETAILED DESCRIPTION OF THIS DISCLOSURE

Introduction

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with the present invention and for all jurisdictions inwhich such incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

As used in this specification, the term “framework type” is used in thesense described in the “Atlas of Zeolite Framework Types,” 2001.

As used herein, the numbering scheme for the Periodic Table Groups isused as in Chemical and Engineering News, 63(5), 27 (1985).

The term “tabular habit” morphology as used herein means a tabularmineral having “parallel stacked thin platelike crystals.” The term“platelet” morphology as used herein means thin platelike crystals.

It will be understood by a person skilled in the art that the MCM-22family material may contain impurities, such as amorphous materials;unit cells having non-MWW framework topologies (e.g., MFI, MTW); and/orother impurities (e.g., heavy metals and/or organic hydrocarbons).Typical examples of the non-MCM-22 family molecular sieve(s) co-existingwith the MCM-22 family molecular sieve(s) of this disclosure areKenyaite, EU-1, ZSM-50, ZSM-12, ZSM-48, ZSM-5, Ferrierite, Mordenite,Sodalite, and/or Analcine. Other examples of the non-MCM-22 familymolecular sieve(s) co-existing with the MCM-22 family molecular sieve(s)of this disclosure are molecular sieves having framework type of EUO,MTW, FER, MOR, SOD, ANA, and/or MFI. The MCM-22 family materials of thisdisclosure are preferably substantially free of non-MCM-22 familymaterial(s). The term “substantially free of non-MCM-22 familymaterial(s)” used herein means the MCM-22 family material of thisdisclosure preferably contains a minor proportion (less than 50 wt %),preferably less than 20 wt %, of non-MCM-22 family materials(“impurities”) in the MCM-22 family materials, which weight percent (wt%) values are based on the combined weight of impurities and pure phaseMCM-22 family materials.

The MCM-22 crystalline material has a composition involving the molarrelationship:X₂O₃:(n)YO₂,wherein X is a trivalent element, such as aluminum, boron, iron and/orgallium, preferably aluminum, Y is a tetravalent element such as siliconand/or germanium, preferably silicon, and n is at least about 10,usually from about 10 to about 150, more usually from about 10 to about60, and even more usually from about 20 to about 40. In theas-synthesized form, the material typically has a formula, on ananhydrous basis and in terms of moles of oxides per n moles of YO₂, asfollows:(0.005−1)M₂O:(1−4)R:X₂O₃ :nYO₂wherein M is an alkali or alkaline earth metal, and R is an organicmoiety. The M and R components are associated with the material as aresult of their presence during synthesis, and are typically removed bypost-synthesis methods well known to those skilled in the art and/orhereinafter more particularly described.

It is to be understood that throughout this detailed description, commoncharacterization techniques were used to describe molecular sievematerials. These common techniques are included ascertaining.

-   -   (a) structure and the degree of crystallinity of the molecular        sieve material by X-Ray Diffraction (XRD); and/or    -   (b) morphology and crystal size of the molecular sieve material        measured by the Scanning Electron Microscope (SEM); and/or    -   (c) chemical composition by atomic absorption spectrometry        and/or Inductively Coupled Plasma Mass Spectrometry (ICP-MS or        ICPMS);    -   (d) adsorption capacities and surface area measured by nitrogen        BET method; and/or    -   (e) catalytic activities and catalytic stabilities measured by        the probing reactions.        X-Ray Powder Diffraction Pattern

The MCM-22 crystalline materials may be distinguished from othercrystalline materials by the X-ray diffraction pattern.

The interplanar spacings, d's, were calculated in Angstrom units (Å),and the relative intensities of the lines, I/I_(o), where the intensityof the strongest line above background, I_(o), is counted as 100, werederived with the use of a profile fitting routine (or second derivativealgorithm). The intensities are uncorrected for Lorentz and polarizationeffects. The relative intensities are given in terms of the symbolsVS=very strong (greater than 60 to 100), S=strong (greater than 40 to60), M=medium (greater than 20 to 40) and W=weak (0 to 20). It should beunderstood that diffraction data listed as single lines may consist ofmultiple overlapping lines which under certain conditions, such asdifferences in crystallographic changes, may appear as resolved orpartially resolved lines. Typically, crystallographic changes caninclude minor changes in unit cell parameters and/or a change in crystalsymmetry, without a change in the structure. These minor effects,including changes in relative intensities, can also occur as a result ofdifferences in cation content, framework composition, nature and degreeof pore filling, and thermal and/or hydrothermal history. Other changesin diffraction patterns can be indicative of important differencesbetween materials, which is the case for comparing MCM-22 with similarmaterials, e.g., MCM-49, MCM-56, and PSH-3.

The interplanar spacings, d's, were considered broad if they exhibitedpeak width of about 1.5° or more at half height determined as 50%intensity value from the maximum to the baseline.

The term “XRD distinguishable peak” as used herein is defined as XRDpeak with clearly defined peak maximum, which is at least two times ofthe average background noise level.

The term “non-discrete” peaks (also “unresolved” peaks) in XRD as usedherein means peaks having a monotonic profile in-between them(successive points either consistently increasing (or staying even) ordecreasing (or staying even) within noise).

The term “discrete” peaks (also “resolved” peaks) in XRD as used hereinmeans XRD peak(s) which are not non-discrete (unresolved).

It should be understood that this X-ray diffraction pattern ischaracteristic of all the species of the present crystallinecomposition. The sodium form as well as other cationic forms revealsubstantially the same pattern with some minor shifts in interplanarspacing and variation in relative intensity. Other minor variations canoccur, depending on the Y to X, e.g., silicon to aluminum, ratio of theparticular sample, as well as its degree of thermal treatment (e.g.,calcination).

The crystalline molecular sieve composition of this disclosure may becharacterized by an X-ray diffraction pattern of the as-synthesizedcrystalline molecular sieve including d-spacing maxima at 13.18±0.25 and12.33±0.23 Angstroms (Table II),

TABLE II Interplanar Relative Intensity, d-Spacing (Å) I/I_(o) × 10013.18 ± 0.25 M-VS 12.33 ± 0.23 M-VSwherein the peak intensity of the d-spacing maximum at 13.18±0.25Angstroms is at least as great as 90% of, preferably at least as greatas 100%, more preferably at least as great as 110% of, the peakintensity of the d-spacing maximum at 12.33±0.23 Angstroms.

The crystalline molecular sieve composition of this disclosure may becharacterized by an X-ray diffraction pattern of the as-synthesizedcrystalline molecular sieve further including d-spacing maxima at11.06±0.18 and 9.25±0.13 Angstroms (Table III),

TABLE III Interplanar Relative Intensity, d-Spacing (Å) I/I_(o) × 10013.18 ± 0.25 M-VS 12.33 ± 0.23 M-VS 11.06 ± 0.18 W-S  9.25 ± 0.13 W-Swherein the peak intensity of the d-spacing maximum at 11.06±0.18Angstroms is at least as great as 90% of, preferably at least as greatas 100%, more preferably at least as great as 110% of, the peakintensity of the d-spacing maximum at 9.25±0.13 Angstroms.

The crystalline molecular sieve composition of this disclosure may becharacterized further by a feature that the d-spacing maxima at11.1±0.18 and 9.3±0.13 Angstroms are non-discrete peaks.

The crystalline molecular sieve composition of this disclosure may becharacterized by an X-ray diffraction pattern of the as-synthesizedcrystalline molecular sieve including d-spacing maxima of as-as listedin Table IV or Table V.

TABLE IV Interplanar Relative Intensity, d-Spacing (Å) I/I_(o) × 10013.18 ± 0.25 M-VS 12.33 ± 0.23 M-VS 11.06 ± 0.18 W-S  9.07 ± 0.13 W-S 3.57 ± 0.06 W-M  3.43 ± 0.06 M-VS

TABLE V Interplanar Relative Intensity, d-Spacing (Å) I/I_(o) × 10013.18 ± 0.25  M-VS 12.33 ± 0.23  M-VS 11.06 ± 0.18  W-S 9.07 ± 0.13 W-S6.57 ± 0.15 W-M 4.41 ± 0.1  W-M, broad 3.96 ± 0.08 W-VS, broad 3.57 ±0.06 W-M 3.43 ± 0.06 M-VS 3.34 ± 0.05 W-SScanning Electron Microscope (SEM)

The SEM image of an MCM-22 molecular sieve produced according to themethod of manufacturing of U.S. Pat. No. 4,954,325 is shown in FIG. 2.The MCM-22 molecular sieve according to method of manufacturing of U.S.Pat. No. 4,954,325 has a thin layered less defined hexagonal plateletsmorphology and an average platelet diameter of less than about 1 μm,determined by the SEM (FIG. 2). The majority of the platelet crystal hasan average platelet diameter of less than about 0.5 micron (μm).

The as-synthesized known MCM-22 crystalline material disclosed in Chem.Lett. Vol. 32, No. 6, page 542-543 (2003) by S. H. Lee, C. H. Shin, andS. B Hong is reported as having a particle size of about 0.5×0.05 μm anda platelet morphology.

The SEM image of a crystalline molecular sieve of this disclosure isshown in FIGS. 4 and 6. The crystalline molecular sieve of thisdisclosure as shown in (FIGS. 4 and 6) has a crystal morphology ofmultilayered platelet aggregates with a majority, preferably at least 50wt %, more preferably at least 75 wt %, of the crystals of thecrystalline molecular sieves, having an average platelet diametergreater than 1 μm. In addition, the crystalline molecular sieve of thisdisclosure (FIGS. 4 and 6) preferably has a crystal morphology ofmultilayered platelet aggregates with a majority, preferably at least 50wt %, more preferably at least 75 wt %, of the crystals of thecrystalline molecular sieves, having an average platelet thickness ofabout 0.025 μm.

Surface Areas and Adsorption Uptake

The overall surface area of a molecular sieve may be measured by theBrunauer-Emmett-Teller (BET) method using adsorption-desorption ofnitrogen (temperature of liquid nitrogen, 77 K). The internal surfacearea may be calculated using t-plot of the Brunauer-Emmett-Teller (BET)measurement. The external surface area is calculated by subtracting theinternal surface area from the overall surface area measured by theBrunauer-Emmett-Teller (BET) measurement.

The crystalline molecular sieve (after calcination) of this disclosuremay be characterized by a preferred total surface area (sum of theexternal and the internal surface areas, as measured by the BET method)of greater than 450 m²/g, preferably greater than 475 m²/g, and morepreferably greater than 500 m²/g.

In addition, the crystalline molecular sieve (after calcination) of thisdisclosure may be characterized by the ratio of the external surfacearea (as measured by the t-plot of BET method) over the total surfacearea of preferably less than 0.15, more preferably less than 0.13, oreven more preferably less than 0.12.

Formulation of the Hydrothermal Reaction Mixtures

Synthetic molecular sieves are often prepared from aqueous hydrothermalreaction mixtures (synthesis mixture(s) or synthetic gel(s)) comprisingsources of appropriate oxides. Organic directing agents may also beincluded in the hydrothermal reaction mixture for the purpose ofinfluencing the production of a molecular sieve having the desiredstructure. The use of such directing agents is discussed in an articleby Lok et al. entitled “The Role of Organic Molecules in Molecular SieveSynthesis” appearing in Zeolites, Vol. 3, October, 1983, pp. 282-291.

After the components of the hydrothermal reaction mixture are properlymixed with one another, the hydrothermal reaction mixture is subjectedto appropriate crystallization conditions. Such conditions usuallyinvolve heating of the hydrothermal reaction mixture to an elevatedtemperature possibly with stirring. Room temperature aging of thehydrothermal reaction mixture is also desirable in some instances.

After the crystallization of the hydrothermal reaction mixture iscomplete, the crystalline product may be recovered from the remainder ofthe hydrothermal reaction mixture, especially the liquid contentsthereof Such recovery may involve filtering the crystals and washingthese crystals with water. However, in order to remove the entireundesired residue of the hydrothermal reaction mixture from thecrystals, it is often necessary to subject the crystals to a hightemperature calcination e.g., at 500° C., possibly in the presence ofoxygen. Such a calcination treatment not only removes water from thecrystals, but this treatment also serves to decompose and/or oxidize theresidue of the organic directing agent which may be occluded in thepores of the crystals, possibly occupying ion exchange sites therein.

The crystalline molecular sieve material of this disclosure may beprepared from a hydrothermal reaction mixture containing sources ofalkali or alkaline earth metal (M), e.g., sodium or potassium, cation,an oxide of trivalent element X, e.g., aluminum, an oxide of tetravalentelement Y, e.g., silicon, an organic (R) directing agent, hereinaftermore particularly described, and water, the hydrothermal reactionmixture having a composition, in terms of mole ratios of oxides, withinthe following ranges:

TABLE VI Reactants Useful Preferred YO₂/X₂O₃ 10 to infinity 15-55H₂O/YO₂ 1 to 10000  5-35 OH⁻/YO₂* 0.001-0.39  0.1-0.35 OH⁻/YO₂**0.001-0.59 0.1-0.5 M/YO₂ 0.001-2   0.1-1   R/YO₂ 0.001-2   0.01-0.5 Seed*** 0-25 wt % 1-5 wt % R Me₆-diquat-5 salt(s) Me₆-diquat-5 salt(s)*The OH⁻/YO₂ of this row is calculated with correction of trivalentelement source. **The OH⁻/YO₂ of this row is calculated withoutcorrection of trivalent element source. ***The weight percent (wt %) ofseed is based on the weight of the solid tetrahedral element oxide.

For these embodiments when reaction mixture for hydrothermal reactionhaving a composition as disclosed in Table VI, the OH⁻:YO₂ molar ratiowithout correction of trivalent element source ranges from about 0.001to about 0.59 and/or OH⁻:YO₂ molar ratio with correction of trivalentelement source ranges from about 0.001 to about 0.39.

The following OH⁻:YO₂ molar ratios (without correction of trivalentelement source) are useful lower OH⁻:YO₂ molar ratio (without correctionof trivalent element source) limits for these embodiments as disclosedin Table VI: 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, and0.55. The following OH⁻:YO₂ molar ratios (without correction oftrivalent element source) are useful upper OH⁻:YO₂ molar ratio (withoutcorrection of trivalent element source) limits for these embodiments asdisclosed in Table VI: 0.59, 0.55, 0.51, 0.5, 0.4, 0.3, 0.2 and 0.1. TheOH⁻:YO₂ molar ratio (without correction of trivalent element source)ideally falls in a range between any one of the above-mentioned lowerlimits and any one of the above-mentioned upper limits, so long as thelower limit is less than or equal to the upper limit. The OH⁻:YO₂ molarratio (without correction of trivalent element source) may be present inan amount ranging from 0.001 to 0.59 in one embodiment, alternatively0.01 to 0.5, alternatively 0.1 to 0.5, alternatively and from 0.1 to 0.4in another embodiment.

The following OH⁻:YO₂ molar ratios (with correction of trivalent elementsource) are useful lower OH⁻:YO₂ molar ratio (with correction oftrivalent element source) limits for these embodiments as disclosed inTable VI: 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, and0.35. The following OH⁻:YO₂ molar ratios (with correction of trivalentelement source) are useful upper OH⁻:YO₂ molar ratio (with correction oftrivalent element source) limits for these embodiments as disclosed inTable VI: 0.39, 0.35, 0.31, 0.3, 0.2 and 0.1. The OH⁻:YO₂ molar ratio(with correction of trivalent element source) ideally falls in a rangebetween any one of the above-mentioned lower limits and any one of theabove-mentioned upper limits, so long as the lower limit is less than orequal to the upper limit. The OH⁻:YO₂ molar ratio (with correction oftrivalent element source) may be present in an amount ranging from 0.001to 0.39 in one embodiment, alternatively 0.01 to 0.35, alternatively 0.1to 0.3, alternatively and from 0.1 to 0.25 in another embodiment.

The crystalline molecular sieve material of this disclosure mayalternatively be prepared from a hydrothermal reaction mixturecontaining sources of alkali or alkaline earth metal (M), e.g., sodiumor potassium, cation, an oxide of trivalent element X, e.g., aluminum,an oxide of tetravalent element Y, e.g., silicon, an organic (R)directing agent, hereinafter more particularly described, and water, thehydrothermal reaction mixture having a composition, in terms of moleratios of oxides, within the following ranges:

TABLE VII Reactants Useful Preferred YO₂/X₂O₃ 10 to infinity   15-55H₂O/YO₂ 1 to 10000   5-35 OH⁻/YO₂*  0.64-2 0.7-2 OH⁻/YO₂**  0.74-2 0.8-2M/YO₂ 0.001-2 0.1-1 R/YO₂ 0.001-2  0.01-0.5 Seed*** 0-25 wt % 1-5 wt % RMe₆-diquat-5 salt(s) Me₆-diquat-5 salt(s) *The OH⁻/YO₂ of this row iscalculated with correction of trivalent element source. **The OH⁻/YO₂ ofthis row is calculated without correction of trivalent element source.***The weight percent (wt %) of seed is based on the weight of the solidtetrahedral element oxide.

For these embodiments when reaction mixture for hydrothermal reactionhaving a composition as disclosed in Table VII, the OH⁻/YO₂ molar ratiowithout correction of trivalent element source ranges from about 0.74 toabout 2 and/or the OH⁻/YO₂ molar ratio with correction of trivalentelement source ranges from about 0.64 to about 2.

The following OH—/YO2 molar ratios (without correction of trivalentelement source) are useful lower OH—/YO2 molar ratio (without correctionof trivalent element source) limits for all disclosure processes: 0.74,0.77, 0.78, 0.80, 0.90, 1 and 1.5. The following OH—/YO2 molar ratios(without correction of trivalent element source) are useful upperOH—/YO2 molar ratio (without correction of trivalent element source)limits for all disclosure processes: 2, 1.6, 1.4, 1.3, 1.2, 1, 0.9 and0.8. The OH—/YO2 molar ratio (without correction of trivalent elementsource) ideally falls in a range between any one of the above-mentionedlower limits and any one of the above-mentioned upper limits, so long asthe lower limit is less than or equal to the upper limit. The OH—/YO2molar ratio (without correction of trivalent element source) may bepresent in an amount ranging from 0.74 to 2 in one embodiment,alternatively 0.8 to 2, alternatively 0.8 to 1, alternatively and from0.8 to 1.1 in another embodiment.

The following OH—/YO2 molar ratios (with correction of trivalent elementsource) are useful lower OH—/YO2 molar ratio (with correction oftrivalent element source) limits for all disclosure processes: 0.64,0.65, 0.66, 0.7, 0.75, 0.80, 0.90, 1 and 1.5. The following OH—/YO2molar ratios (with correction of trivalent element source) are usefulupper OH—/YO2 molar ratio (with correction of trivalent element source)limits for all disclosure processes: 2, 1.6, 1.4, 1.3, 1.2, 1, 0.9 and0.8. The OH—/YO2 molar ratio (with correction of trivalent elementsource) ideally falls in a range between any one of the above-mentionedlower limits and any one of the above-mentioned upper limits, so long asthe lower limit is less than or equal to the upper limit. The OH—/YO2molar ratio (with correction of trivalent element source) may be presentin an amount ranging from 0.74 to 2 in one embodiment, alternatively 0.8to 2, alternatively 0.8 to 1, alternatively and from 0.8 to 1.1 inanother embodiment.

The crystalline molecular sieve material of this disclosure mayalternatively be prepared from a hydrothermal reaction mixturecontaining sources of alkali or alkaline earth metal (M), e.g., sodiumor potassium, cation, an oxide of trivalent element X, e.g., aluminum,an oxide of tetravalent element Y, e.g., silicon, an organic (R)directing agent, hereinafter more particularly described, and water, thehydrothermal reaction mixture having a composition, in terms of moleratios of oxides, within the following ranges:

TABLE VIII Reactants Useful Preferred YO₂/X₂O₃ 10 to infinity 15-55H₂O/YO₂    5-35  5-30 OH⁻/YO₂* 0.001-2 0.001-2    M/YO₂ 0.001-2 0.1-1  R/YO₂ 0.001-2 0.01-0.5  Seed** 0-25 wt % 1-5 wt % R Me₆-diquat-5 salt(s)Me₆-diquat-5 salt(s) *The OH⁻/YO₂ of this row is calculated with orwitout correction of trivalent element source. **The weight percent (wt%) of seed is based on the weight of the solid tetrahedral elementoxide.

The sources of the various elements required in the final product may beany of those in commercial use or described in the literature, as maythe method of preparation of the synthesis mixture.

Y is a tetravalent element selected from Groups 4-14 of the PeriodicTable of the Elements, such as silicon and/or germanium, preferablysilicon. In some embodiments of this disclosure, the source of YO₂comprises solid YO₂, preferably about 30 wt % solid YO₂ in order toobtain the crystal product of this disclosure. When YO₂ is silica, theuse of a silica source containing preferably about 30 wt % solid silica,e.g., silica sold by Degussa under the trade names Aerosil or Ultrasil(a precipitated, spray dried silica containing about 90 wt % silica), anaqueous colloidal suspension of silica, for example one sold by GraceDavison under the trade name Ludox, or HiSil (a precipitated hydratedSiO₂ containing about 87 wt % silica, about 6 wt % free H₂O and about4.5 wt % bound H₂O of hydration and having a particle size of about 0.02micron) favors crystal formation from the above mixture. Preferably,therefore, the YO₂, e.g., silica, source contains about 30 wt % solidYO₂, e.g., silica, and more preferably about 40 wt % solid YO₂, e.g.,silica. The source of silicon may also be a silicate, e.g., an alkalimetal silicate, or a tetraalkyl orthosilicate.

In additional embodiments of this disclosure, the source of YO₂comprises acid of the tetravalent element (Y). When YO₂ is silica, thesilica source may be silicic acid.

X is a trivalent element selected from Groups 3-13 of the Periodic Tableof the Elements, such as aluminum, and/or boron, and/or iron and/orgallium, preferably aluminum. The source of X2O3, e.g., aluminum, ispreferably aluminum sulphate or hydrated alumina. Other aluminum sourcesinclude, for example, other water-soluble aluminum salts, sodiumaluminate, or an alkoxide, e.g., aluminum isopropoxide, or aluminummetal, e.g., in the form of chips.

The alkali or alkali earth metal element is advantageously lithium,sodium, potassium, calcium, or magnesium. The source of alkali or alkaliearth metal element is advantageously being metal oxide, metal chloride,metal fluoride, metal sulfate, metal nitrate, or metal aluminate. Thesodium source advantageously being sodium hydroxide or sodium aluminate.The alkali metal may also be replaced by ammonium (NH₄ ⁺) or itsequivalents, e.g., alkyl-ammonium ion.

In some embodiments of this disclosure, the M:YO2, e.g., M:SiO2 molarratio ranges from a low value of 0.001, preferably 0.01, and optionally0.1, to a high value of 2.0, preferably 1, and optionally 0.5. TheM:YO2, e.g., M:SiO2 molar ratio ideally falls in a range comprising anycombination of the above-mentioned low value(s) and the above-mentionedhigh values(s).

In some embodiments of this disclosure, the H2O:YO2, e.g., H2O:SiO2molar ratio ranges from a low value of 1, preferably 5, and optionally10, to a high value of 10000, preferably 5000, and optionally 500. TheH2O:YO2, e.g., H2O:SiO2 molar ratio ideally falls in a range comprisingany combination of the above-mentioned low value(s) and theabove-mentioned high values(s).

The OH—:YO2 molar ratio (without correction of trivalent element source)as used in this disclosure does not include correction of acid in thereaction mixture for hydrothermal reaction. It is calculated based onthe total mole of hydroxide added to the reaction mixture forhydrothermal reaction divided by the total mole of Y element added tothe reaction mixture for hydrothermal reaction. The hydroxide (OH—)source is advantageously alkali metal oxide, e.g., Li2O, Na2O, K2O,Rb2O, Cs2O, Fr2O, or any combination thereof; alkali metal hydroxide,e.g., LiOH, NaOH, KOH, RbOH, CsOH, FrOH, or any combination thereof;ammonium hydroxide, alkali earth metal oxide, e.g., BeO, MgO, CaO, SrO,BaO, RaO, or any combination thereof; alkali earth metal hydroxide,e.g., Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2, Ra(OH)2, or anycombination thereof; oxide(s) or hydroxide(s) of any element selectedfrom Groups 3-17, and any combination thereof; and organic hydroxide(s),such as quarterly ammonium hydroxide(s), hydroxide of organic template(R) used in the synthesis.

The OH⁻:YO₂ molar ratio (with correction of trivalent element source) asused in this disclosure include correction of acid in the reactionmixture for hydrothermal reaction. The mole of OH⁻ after correction iscalculated by subtracting three times the mole of trivalent element (ifthe trivalent element source is supplied in the form of salt other thanoxide, hydroxide, or metal) from the total mole of hydroxide added tothe reaction mixture for hydrothermal reaction. The OH⁻:YO₂ molar ratio(with correction of trivalent element source) is, therefore, calculatedbased on the total mole of hydroxide after correction divided by thetotal mole of Y element added to the reaction mixture for hydrothermalreaction.

In some embodiments of this disclosure, the OH⁻:YO₂, e.g., OH⁻:SiO₂molar ratio ranges from a low value of 0.001, preferably 0.01, andoptionally 0.1, to a high value of 2.0, preferably 1, and optionally0.5. The OH⁻:YO₂, e.g., OH⁻:SiO₂ molar ratio ideally falls in a rangecomprising any combination of the above-mentioned low value(s) and theabove-mentioned high values(s).

Directing agent R comprises at least one ofN,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium (Me6-diquat-5) salt, e.g.,Me6-diquat-5 salt of hydroxide, chloride, bromide, fluoride, nitrate,sulfate, phosphate, or any mixture thereof.

In some embodiment, the directing agent R is selected from the groupconsisting of Me6-diquat-5 dibromide, Me6-diquat-5 dichloride,Me6-diquat-5 difluoride, Me6-diquat-5 diiodide, Me6-diquat-5dihydroxide, Me6-diquat-5 sulfate, Me6-diquat-5 dinitrate, Me6-diquat-5hydroxide bromide, Me6-diquat-5 hydroxide chloride, Me6-diquat-5hydroxide fluoride, Me6-diquat-5 hydroxide iodide, Me6-diquat-5hydroxide nitrate, Me6-diquat-5 fluoride bromide, Me6-diquat-5 fluoridechloride, Me6-diquat-5 fluoride iodide, Me6-diquat-5 fluoride nitrate,Me6-diquat-5 chloride bromide, Me6-diquat-5 chloride iodide,Me6-diquat-5 chloride nitrate, Me6-diquat-5 iodide bromide, Me6-diquat-5bromide nitrate, and any mixtures thereof.

A factor affecting the cost and the product quality of the synthesis ofa crystalline molecular sieve is the amount of the directing agent(represented by the R:YO₂; e.g., R:SiO₂ molar ratio). The directingagent is generally the most expensive reactant(s) in the hydrothermalreaction mixture of many crystalline molecular sieves. The lower theamount of the directing agent in the hydrothermal reaction mixture (lowR:YO₂; e.g., R:SiO₂ molar ratio), the cheaper the final molecular sieveproduced.

In some embodiments of this disclosure, the R:YO2; e.g., R:SiO2 molarratio ranges from a low value of 0.001, preferably 0.05, and optionally0.1, to a high value of 2.0, preferably 0.5, and optionally 0.15. TheR:YO₂; e.g., R:SiO₂ molar ratio ideally falls in a range comprising anycombination of the above-mentioned low value(s) and the above-mentionedhigh value(s).

It should be realized that the hydrothermal reaction mixture componentscan be supplied by more than one source. The hydrothermal reactionmixture can be prepared either batchwise or continuously. Crystal sizeand crystallization time of the crystalline molecular sieve of thisdisclosure may vary with the nature of the hydrothermal reaction mixtureemployed and the crystallization conditions.

It will be understood by a person skilled in the art that the synthesismixture having a composition within the molar ranges as discussed abovemeans that the synthesis mixture is the product of mixing, adding,reacting, or by any means of providing such a mixture, wherein suchproduct has a composition within the molar ranges as discussed above.The product of mixing, adding, reacting, or by any means of providingsuch a mixture may or may not contain individual ingredients when thesynthesis mixture was prepared. The product of mixing, adding, reacting,or by any means of providing such a mixture, may even contain reactionproduct of individual ingredients when the synthesis mixture wasprepared by mixing, adding, reacting, or by any means of providing sucha mixture.

Optionally the hydrothermal reaction mixture may contain seed crystals.It is well known that seeding a molecular sieve synthesis mixturefrequently has beneficial effects, for example in controlling theparticle size of the product, avoiding the need for an organic template,accelerating synthesis, and improving the proportion of product that isof the intended framework type. In some embodiments of this disclosure,the synthesis of the crystalline molecular sieve is facilitated by thepresence of 0 to about 25 wt %, preferably about 1 to about 5 wt %, seedcrystals based on total weight of tetrahedral element oxide (e.g.,silica) of the hydrothermal reaction mixture.

Usually the seeding crystals are from the synthesis similar to the onewhere they are used. In general any form of the crystalline material maybe useful in facilitating synthesis on the new phase.

Crystallization Conditions

Crystallization of the crystalline molecular sieve of this disclosurecan be carried out at either static or stirred condition in a reactorvessel, such as for example, autoclaves. The total useful range oftemperatures for crystallization is from about 100° C. to about 200° C.for a time sufficient for crystallization to occur at the temperatureused, e.g., from about 1 hour to about 400 hours, optionally withagitation of 0-1000 rotation per minutes (RPM). Preferably, the range oftemperatures for crystallization is from about 140° C. to about 180° C.for a time sufficient for crystallization to occur at the temperatureused, e.g., from about 1 hour to about 200 hours, optionally withagitation of 0-400 RPM.

Thereafter, the crystals are separated from the liquid and recovered.The procedure may include an aging period, either at room temperature(˜25° C.) or, preferably, at a moderately elevated temperature, beforethe hydrothermal treatment (“hydrothermal reaction”) at more elevatedtemperature. The latter may include a period of gradual or stepwisevariation in temperature.

Optionally, the hydrothermal reaction is carried out with any type ofagitation, e.g., stirring or rotating the vessel about a horizontal axis(tumbling). The rate of the agitation is ranged from 0 to about 1000RPM, preferably from 0 to about 400 RPM.

In some embodiments, the crystalline molecular sieve of this disclosureis an MCM-22 family material. In some preferred embodiments, thecrystalline molecular sieve of this disclosure comprises at least one ofMCM-22, MCM-49, MCM-56, an intergrowth-phase of MCM-22, and/or MCM-49,and/or MCM-56, or a mix phase of MCM-22, and/or MCM-49, and/or MCM-56.

The molecular sieve product from the synthesis may further be filtrated,washed with water, and/or dried. The crystalline molecular sieve formedby crystallization may be recovered and subjected for further treatment,such as, ion-exchange with ammonium salt(s) (e.g., ammonium hydroxide,ammonium nitrate, ammonium chloride, ammonium sulfate, ammoniumphosphate, or any combination thereof) and/or calcination in anoxidative atmosphere (e.g., air, gas with an oxygen partial pressure ofgreater than 0 kPa-a) at a temperature of greater than 200° C.,preferably at least 300° C., more preferably at least 400° C., and mostpreferably at least 500° C.

Catalysis and Adsorption

A summary of the molecular sieves and/or zeolites, in terms ofproduction, modification and characterization of molecular sieves, isdescribed in the book “Molecular Sieves—Principles of Synthesis andIdentification”; (R. Szostak, Blackie Academic & Professional, London,1998, Second Edition). In addition to molecular sieves, amorphousmaterials, chiefly silica, aluminum silicate and aluminum oxide, havebeen used as adsorbents and catalyst supports. A number of long-knownforming techniques, like spray drying, prilling, pelletizing andextrusion, have been and are being used to produce macrostructures inthe form of, for example, spherical particles, extrudates, pellets andTablets of both micropores and other types of porous materials for usein catalysis, adsorption and ion exchange. A summary of these techniquesis described in “Catalyst Manufacture,” A. B. Stiles and T. A. Koch,Marcel Dekker, New York, 1995.

To the extent desired, the original metal cations of the as-synthesizedmaterial can be replaced in accordance with techniques well known in theart, at least in part, by ion exchange with other cations. Preferredreplacing cations include metal ions, hydrogen ions, hydrogen precursor,e.g., ammonium, ions and mixtures thereof. Particularly preferredcations are those which tailor the catalytic activity for certainhydrocarbon conversion reactions. These include hydrogen, rare earthmetals and metals of Groups 1-17, preferably Groups 2-12 of the PeriodicTable of the Elements.

The crystalline molecular sieve of this disclosure, preferably theMCM-22 family molecular sieve, when employed either as an adsorbent oras a catalyst in an organic compound conversion process should begenerally dehydrated, at least partially. This can be done by heating toa temperature in the range of e.g., 200° C. to 595° C. in an atmospheresuch as air or nitrogen, and at atmospheric, sub-atmospheric orsuper-atmospheric pressures for e.g., between 30 minutes and 48 hours.The degree of dehydration is measured by the percentage of weight lossrelative to the total weight loss of a molecular sieve sample at 595° C.under flowing dry nitrogen (less than 0.001 kPa partial pressure ofwater vapor) for 48 hours. Dehydration can also be performed at roomtemperature (˜25° C.) merely by placing the silicate in a vacuum, but alonger time is required to obtain a sufficient amount of dehydration.

When used as a catalyst, the crystalline molecular sieve of thisdisclosure, preferably the MCM-22 family molecular sieve, should begenerally subjected to thermal treatment to remove part or all of anyorganic constituent. The crystalline molecular sieve of this disclosure,preferably the MCM-22 family molecular sieve, can also be used as acatalyst in intimate combination with a hydrogenating component such astungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium,manganese, or a noble metal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be in the composition by way of co-crystallization,exchanged into the composition to the extent a Group 13 element, e.g.,aluminum, is in the structure, impregnated therein or intimatelyphysically admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating thesilicate with a solution containing a platinum metal-containing ion.Thus, suitable platinum compounds for this purpose includechloroplatinic acid, platinous chloride and various compounds containingthe platinum amine complex.

The above crystalline molecular sieve, preferably the MCM-22 familymolecular sieve, especially in its metal, hydrogen and ammonium formscan be beneficially converted to another form by thermal treatment. Thisthermal treatment is generally performed by heating one of these formsat a temperature of at least 370° C. for at least 1 minute and generallynot longer than 1000 hours. While sub-atmospheric pressure can beemployed for the thermal treatment, atmospheric pressure is desired forreasons of convenience. The thermal treatment can be performed at atemperature up to about 925° C. The thermal treated product isparticularly useful in the catalysis of certain hydrocarbon conversionreactions. The thermally treated product, especially in its metal,hydrogen and ammonium forms, is particularly useful in the catalysis ofcertain organic, e.g., hydrocarbon, conversion reactions. Non-limitingexamples of such reactions include those described in U.S. Pat. Nos.4,954,325; 4,973,784; 4,992,611; 4,956,514; 4,962,250; 4,982,033;4,962,257; 4,962,256; 4,992,606; 4,954,663; 4,992,615; 4,983,276;4,982,040; 4,962,239; 4,968,402; 5,000,839; 5,001,296; 4,986,894;5,001,295; 5,001,283; 5,012,033; 5,019,670; 5,019,665; 5,019,664; and5,013,422, each incorporated herein by reference as to the descriptionof the catalytic reactions.

The crystals prepared by the instant invention can be shaped into a widevariety of particle sizes. Generally speaking, the particles can be inthe form of a powder, a granule, or a molded product, such as anextrudate. In cases where the catalyst is molded, such as by extrusion,the crystals can be extruded before drying or partially dried and thenextruded.

The crystalline molecular sieve(s) of this disclosure, preferably theMCM-22 family molecular sieve(s), may be used as an adsorbent, such asfor separating at least one component from a mixture of components inthe vapor or liquid phase having differential sorption characteristicswith respect to the crystalline molecular sieve(s) of this disclosure.Therefore, at least one component can be partially or substantiallytotally separated from a mixture of components having differentialsorption characteristics with respect to the crystalline molecularsieve(s) of this disclosure by contacting the mixture with thecrystalline molecular sieve(s) of this disclosure to selectively sorbthe one component.

The crystalline molecular sieve(s) of this disclosure, preferably theMCM-22 family molecular sieve(s) of this disclosure, are useful ascatalyst in a wide range of processes, including separation processesand hydrocarbon conversion processes. Specific examples of hydrocarbonconversion processes which are effectively catalyzed by the crystallinemolecular sieve(s) of this disclosure, preferably the MCM-22 familymolecular sieve(s) of this disclosure, by itself or in combination withone or more other catalytically active substances including othercrystalline catalysts, include the following:

-   (i) alkylation of aromatic hydrocarbons, e.g., benzene, with long    chain olefins, e.g., C₁₄ olefin, with reaction conditions including,    individually or in any combination, a temperature of from about    340° C. to about 500° C., a pressure of from about 101 to about    20200 kPa-a (absolute), a weight hourly space velocity of from about    2 hr⁻¹ to about 2000 hr⁻¹ and an aromatic hydrocarbon/olefin mole    ratio of from about 1/1 to about 20/1, to provide long chain alkyl    aromatics which can be subsequently sulfonated to provide synthetic    detergents;-   (ii) alkylation of aromatic hydrocarbons with gaseous olefins to    provide short chain alkyl aromatic compounds, e.g., the alkylation    of benzene with propylene to provide cumene, with reaction    conditions including, individually or in any combination, a    temperature of from about 10° C. to about 125° C., a pressure of    from about 101 to about 3030 kPa-a, and an aromatic hydrocarbon    weight hourly space velocity (WHSV) of from 5 hr⁻¹ to about 50 hr⁻¹;-   (iii) alkylation of reformate containing substantial quantities of    benzene and toluene with fuel gas containing C₅ olefins to provide,    inter alia, mono- and di-alkylates with reaction conditions    including, individually or in any combination, a temperature of from    about 315° C. to about 455° C., a pressure of from about 3000 to    about 6000 kPa-a, a WHSV-olefin of from about 0.4 hr⁻¹ to about 0.8    hr⁻¹, a WHSV-reformate of from about 1 hr⁻¹ to about 2 hr⁻¹ and a    gas recycle of from about 1.5 to 2.5 vol/vol fuel gas feed;-   (iv) alkylation of aromatic hydrocarbons, e.g., benzene, toluene,    xylene and naphthalene, with long chain olefins, e.g., C₁₄ olefin,    to provide alkylated aromatic lube base stocks with reaction    conditions including, individually or in any combination, a    temperature of from about 160° C. to about 260° C. and a pressure of    from about 2600 to 3500 kPa-a;-   (v) alkylation of phenols with olefins or equivalent alcohols to    provide long chain alkyl phenols with reaction conditions including,    individually or in any combination, a temperature of from about    200° C. to about 250° C., a pressure of from about 1500 to 2300    kPa-a and a total WHSV of from about 2 hr⁻¹ to about 10 hr⁻¹;-   (vi) conversion of light paraffins to olefins and aromatics with    reaction conditions including, individually or in any combination, a    temperature of from about 425° C. to about 760° C. and a pressure of    from about 170 to about 15000 kPa-a;-   (vii) conversion of light olefins to gasoline, distillate and lube    range hydrocarbons with reaction conditions including, individually    or in any combination, a temperature of from about 175° C. to about    375° C. and a pressure of from about 800 to about 15000 kPa-a;-   (viii) two-stage hydrocracking for upgrading hydrocarbon streams    having initial boiling points above about 260° C. to premium    distillate and gasoline boiling range products in a first stage    using the MCM-22 family molecular sieve of this disclosure in    combination with a Groups 8-10 metal as catalyst with effluent    therefrom being reaction in a second stage using zeolite Beta, also    in combination with a Groups 8-10 metal, as catalyst, the reaction    conditions including, individually or in any combination, a    temperature of from about 340° C. to about 455° C., a pressure of    from about 3000 to about 18000 kPa-a, a hydrogen circulation of from    about 176 to about 1760 liter/liter and a liquid hourly space    velocity (LHSV) of from about 0.1 to 10 h⁻¹;-   (ix) a combination hydrocracking/dewaxing process in the presence of    the MCM-22 family molecular sieve of this disclosure and a    hydrogenation component as catalyst, or a mixture of such catalyst    and zeolite Beta, with reaction conditions including, individually    or in any combination, a temperature of from about 350° C. to about    400° C., a pressure of from about 10000 to about 11000 kPa-a, an    LHSV of from about 0.4 to about 0.6 and a hydrogen circulation of    from about 528 to about 880 liter/liter;-   (x) reaction of alcohols with olefins to provide mixed ethers, e.g.,    the reaction of methanol with isobutene and/or isopentene to provide    methyl-t-butyl ether (MTBE) and/or t-amyl methyl ether (TAM) with    conversion conditions including, individually or in any combination,    a temperature of from about 20° C. to about 200° C., a pressure of    from 200 to about 20000 kPa-a, a WHSV (gram-olefin per hour    gram-zeolite) of from about 0.1 hr⁻¹ to about 200 hr⁻¹ and an    alcohol to olefin molar feed ratio of from about 0.1/1 to about 5/1;-   (xi) toluene disproportionation with C₉+ aromatics as co-feed with    reaction conditions including, individually or in any combination, a    temperature of from about 315° C. to about 595° C., a pressure of    from about 101 to about 7200 kPa-a, a hydrogen/hydrocarbon mole    ratio of from about 0 (no added hydrogen) to about 10 and a WHSV of    from about 0.1 hr⁻¹ to about 30 hr⁻¹;-   (xii) preparation of the pharmaceutically-active compound    2-(4-isobutylphenyl) propionic acid, i.e. ibuprofen, by reacting    isobutyl benzene with propylene oxide to provide the intermediate    2-(4-isobutylphenyl) propanol followed by oxidation of the alcohol    to the corresponding carboxylic acid;-   (xiii) use as an acid-binding agent in the reaction of amines with    heterocyclic fiber-reactive components in preparation of dyes to    prepare practically salt-free reactive dye-containing solution, as    in German Patent No. DE 3,625,693, incorporated entirely herein by    reference;-   (xiv) as the absorbent for separating 2,6-toluene diisocyanate    (2,6-TDI) from isomers if TDI as in U.S. Pat. No. 4,721,807,    incorporated entirely herein by reference, whereby a feed mixture    comprising 2,6-TDI and 2,4-TDI is contacted with the present MCM-22    family molecular sieve which has been cation-exchanged with K ions    to absorb the 2,6-TDI, followed by recovering the 2,6-TDI by    desorption with desorbent material comprising toluene;-   (xv) as the absorbent for separating 2,4-TDI from its isomers as in    U.S. Pat. No. 4,721,806, incorporated entirely herein by reference,    whereby a feed mixture comprising 2,4-TDI and 2,6-TDI is contact    with the present MCM-22 family molecular sieve which has been    cation-exchanged with Na, Ca Li and/or Mg ions to absorb the    2,4-TDI, followed by recovering the 2,4-TDI by desorption with    desorbent material comprising toluene; and-   (xvi) in a process for decreasing the durene content of a 90-200°    C.+ bottoms fraction obtained from the catalytic conversion of    methanol to gasoline which comprises contacting the    durene-containing bottoms fraction with hydrogen over a catalyst of    the present MCM-22 family molecular sieve with a hydrogenation    metal, at conditions including, individually or in any combination,    a temperature of from about 230° C. to about 425° C. and a pressure    of from about 457 to about 22000 kPa-a.

In an embodiment, the crystalline molecular sieve(s) of this disclosure,preferably the MCM-22 family molecular sieve(s) of this disclosure, maybe used in processes that co-produce phenol and ketones that proceedthrough benzene alkylation, followed by formation of the alkylbenzenehydroperoxide and cleavage of the alkylbenzene hydroperoxide into phenoland ketone. In such processes, the crystalline molecular sieve(s) ofthis disclosure, preferably the MCM-22 family molecular sieve(s) of thisdisclosure, are used in the first step, that is, benzene alkylation.Examples of such processes includes processes in which benzene andpropylene are converted to phenol and acetone, benzene and C₄ olefinsare converted to phenol and methyl ethyl ketone, such as those describedfor example in international application PCT/EP2005/008557, benzene,propylene and C₄ olefins are converted to phenol, acetone and methylethyl ketone, which, in this case can be followed by conversion ofphenol and acetone to bis-phenol-A as described in internationalapplication PCT/EP2005/008554, benzene is converted to phenol andcyclohexanone, or benzene and ethylene are converted to phenol andmethyl ethyl ketone, as described for example in PCT/EP2005/008551.

The crystalline molecular sieve(s) of this disclosure, preferably theMCM-22 family molecular sieve(s) of this disclosure, are useful inbenzene alkylation reactions where selectivity to the monoalkylbenzeneis required. Furthermore, the crystalline molecular sieve(s) of thisdisclosure, preferably the MCM-22 family molecular sieve(s) of thisdisclosure, is particularly useful to produce selectivelysec-butylbenzene from benzene and C₄ olefin feeds that are rich inlinear butenes, as described in international applicationPCT/EP2005/008557. Preferably, this conversion is carried out byco-feeding benzene and the C₄ olefin feed with the catalyst of thepresent invention, at a temperature of about 60° C. to about 260° C.,for example of about 100° C. to 200° C., a pressure of 7000 kPa-a orless, and a feed weight hourly space velocity (WHSV) based on C₄alkylating agent of from about 0.1 to 50 h⁻¹ and a molar ratio ofbenzene to C₄ alkylating agent from about 1 to about 50.

The crystalline molecular sieve(s) of this disclosure, preferably theMCM-22 family molecular sieve(s) of this disclosure, are also usefulcatalyst for transalkylations, such as, for example, polyalkylbenzenetransalkylations.

In the case of many catalysts, it is desired to incorporate the newcrystal with another material resistant to the temperatures and otherconditions employed in organic conversion processes. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Use of a material in conjunctionwith the new crystal, i.e. combined therewith or present duringsynthesis of the new crystal, which is active, tends to change theconversion and/or selectivity of the catalyst in certain organicconversion processes. Inactive materials suitably serve as diluents tocontrol the amount of conversion in a given process so that products canbe obtained economically and orderly without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays, e.g., bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. The materials, i.e. clays, oxides, etc., function as bindersfor the catalyst. It is desirable to provide a catalyst having goodcrush strength because in commercial use it is desirable to prevent thecatalyst from breaking down into powder-like materials. These claybinders have been employed normally only for the purpose of improvingthe crush strength of the catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dictite, narcite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with the present crystal also includeinorganic oxides, notably alumina.

In addition to the foregoing materials, the new crystal can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided crystalline molecular sieveand inorganic oxide matrix vary widely, with the crystal content rangingfrom about 1 to about 99 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 20 to about 80 wt % of the composite.

These and other facets of the present invention is exemplified by thefollowing Examples.

EXAMPLES

In the Examples, the XRD diffraction patterns of the as-synthesizedmaterials were recorded on a Bruker D4 X-Ray Powder Diffractometer usingcopper Kα radiation in the 2θ range of 2 to 40 degrees.

The SEM images were obtained on a HITACHI 54800 Field Emission ScanningElectron Microscope (SEM). The crystal size was measured by averagingthe size of multiple crystals as shown in the SEM.

The crystallinity is defined as the ratio of the sum of the two mainpeaks, 7.1 and 26 (2θ), to the ratio of the sum of the same peaks in thestandard (reference Example for a given synthesis formulation andconditions), multiplied by 100.

The BET surface area was measured by Micromeritics TriStar 3000 V6.05A(Micromeritics Corporation, Norcross, Ga.) with sample pretreated at350° C. in air.

The external surface area over overall BET surface area ratio wascalculated from the t-plot generated as part of the BET determination bynitrogen sorption.

The following Examples illustrate exemplary preferred embodiments:

Example A

In this example, MCM-22 was prepared according to the method of U.S.Pat. No. 4,954,325.

A hydrothermal reaction mixture was prepared from water,hexamethyleneimine (HMI) (Sigma-Aldrich Company), silica (Ultrasil™,Degussa Corp.), 45 wt % sodium aluminate solution (25.5% Al2O3, 19.5%Na2O; USALCO), and 50 wt % sodium hydroxide solution. The mixture hadthe following molar composition as shown in Table IX:

TABLE IX Example A Molar composition SiO₂/Al₂O₃ 30 H₂O/SiO₂ 20 OH⁻/SiO₂*0.17 Na⁺/SiO₂ 0.17 HMI/SiO₂ 0.35 Crystallization conditions Temperature(° C.) 143 Stirring speed (RPM) 250 Time (hr) 72 Characterizations XRDResult Pure Phase MCM-22 (FIG. 1) Crystallinity (%) 100 SiO₂/Al₂O₃(molar ratio) 23 Total Surface Area (m²/g) 604 Micropore Surface Area(m²/g) 506 External Surface Area (m²/g) 98 Crystal size (SEM) 0.5 ×0.025 μm plates (FIG. 2) *The OH⁻/SiO₂ of this row is calculated withoutcorrection of trivalent element source since aluminum was suplied asAl₂O₃.

The hydrothermal reaction mixture was crystallized according to theconditions listed in the Table IX. The XRD of the as-synthesizedmaterial of Example A (FIG. 1) showed pure phase MCM-22. The SEM pictureof the material of Example A (FIG. 2) showed a platelet morphology withan average crystal size of 0.5×0.025 μm. After calcination, the materialexhibited an XRD according to that reported in U.S. Pat. No. 4,954,325.

Examples 1-2

Hydrothermal reaction mixtures were prepared from water, Me₆-diquat-5(“R”) dibromide (SACHEM, Inc.), silica (Ultrasil™, Degussa Corp.),aluminum sulfate solution (8.1% Al₂O₃) solution, and 50 wt % sodiumhydroxide solution. The mixtures had the following molar compositions asshown in Table X:

TABLE X Example 1 Example 2 Molar composition SiO₂/Al₂O₃ 30 32 H₂O/SiO₂21 34 OH⁻/SiO₂* 0.28 0.47 Na⁺/SiO₂ 0.48 0.66 R/SiO₂ 0.15 0.15Crystallization conditions Temperature (° C.) 170 160 Stirring speed(RPM) 0 0 Time (hr) 80 220 Characterizations XRD Result See FIG. 3 SeeFIG. 5 SiO₂/Al₂O₃ (molar ratio) 24 N/A BET area (m²/g) 557 N/A Crystalsize (SEM) >1 μm >1 μm wide (FIG. 4) (FIG. 6) Platelet Thickness (SEM)~0.025 μm ~0.025 μm (FIG. 4) (FIG. 6) *The OH⁻/SiO₂ of this row iscalculated with correction of trivalent element source since aluminumwas suplied as aluminum salt.

The mixture of Example 1 was crystallized at 170° C. in a Teflon™ bottlewith no stirring for 80 hours. After crystallization, the hydrothermalreaction mixture slurry of Example 1 was filtered. The as-synthesizedmaterial had an XRD pattern shown in FIG. 3.

The mixture of Example 2 was crystallized at 160° C. in a Teflon™ bottlewith no stirring for 220 hours. After crystallization, the hydrothermalreaction mixture slurry of Example 2 was filtered. The as-synthesizedmaterial had an XRD pattern shown in FIG. 5.

The crystalline molecular sieve made in Examples 1 and 2 showed XRDdiffractions of pure phase MCM-22 family molecular sieve. The XRDdiffraction of the crystalline molecular sieve of Examples 1 and 2included d-spacing maxima at 13.18±0.25 and 12.33±0.23 Angstroms,wherein the peak intensity of the d-spacing maximum at 13.18±0.25Angstroms is approximately equal or higher than the peak intensity ofthe d-spacing maximum at 12.33±0.23 Angstroms. The XRD diffraction ofthe crystalline molecular sieve of Examples 1 and 2 further includedd-spacing maxima at 11.06±0.18 and 9.25±0.13 Angstroms, wherein the peakintensity of the d-spacing maximum at 11.06±0.18 Angstroms isapproximately equal or higher than the peak intensity of the d-spacingmaximum at 9.25±0.13 Angstroms. Additionally, the d-spacing maxima at11.06±0.18 and 9.25±0.13 Angstroms were non-discrete peaks.

Further, the XRD diffractions of the crystalline molecular sieve ofExamples 1 and 2 were further characterized by including valuessubstantially as shown in Tables II, III, IV, or V.

Example 3

100 grams of 1 M ammonium nitrate solution was mixed with 13 grams ofsolid from Example 1 (water washed and dried). The mixture was stirredat room temperature (˜25° C.) for one hour and filtrated. Another 100grams of 1 M ammonium nitrate solution was mixed with the filtratedsolid from the previous step and stirred at room temperature (˜25° C.)for one hour. The mixture was filtered and washed with water. Thefiltrated and washed solid was dried in an oven for 24 hours at 110° C.

Example 4

The synthesis was carried out in a manner similar to Example 1 exceptfor time of crystallization of 60 hrs. A small sample revealed a fullycrystalline product. 400 ml of water was added to the slurry, agitatedand supernatant decanted after the solids settled. Water was addedagain, stirred and the slurry filtered and washed. The finalas-synthesized solid product was dried at 121° C. (250° F.).

15 g of the as-synthesized product was exchanged with ammonium nitrateusing 100 g of ammonium nitrate like in Example 4. A portion wascalcined in air at 540° C. affording the calcined product with BETsurface area of 514 m²/g, external surface area 72 m²/g and the ratioexternal to total area equal to 0.14.

The X-ray diffraction patterns for the as-synthesized, and ammoniumexchanged and calcined materials of Example 4, are shown in FIG. 7.

Example 5

A catalyst was prepared from 80 weight parts of product of Example 1mixed with 20 weight parts of alumina (LaRoche Versal 300) on a drybasis. The catalyst was slurried in ammonium nitrate, filtered and driedat 120° C. before use. The catalyst was activated by calcining innitrogen at 540° C., followed by aqueous ammonium nitrate exchange andcalcining in air at 540° C.

Example 6

A catalyst was prepared from 80 weight parts of product of ComparativeExample A mixed with 20 weight parts of alumina (LaRoche Versal 300) onthe dry basis. Water was added to the mixture to allow the resultingcatalyst to be formed into extrudates. The prepared extrudates weredried at 120° C. before use. The catalyst was activated by calcining innitrogen at 540° C., followed by aqueous ammonium nitrate exchange andcalcining in air at 540° C.

Example 7

The catalysts prepared in Example 5 and Example 6 were sized to 14/24mesh and tested for benzene alkylation with propylene. Benzenealkylation with propylene was conducted using the catalysts prepared inExamples 5 and 6. The catalyst was loaded into a catalyst basket into awell-mixed Parr autoclave reactor. Benzene (156.1 grams) and propylene(28.1 grams) were then added in a 3:1 molar ratio of benzene:propylene.The reaction conditions were 130° C. at 2183 kPa-a (300 psig) and thereaction was run for 4 hours. A small sample of product was withdrawn atregular intervals and analyzed using an off-line GC (Model HP 5890). Thecatalyst performance was assessed by a kinetic activity rate constantbased on propylene conversion and selectivity to cumene at 100%propylene conversion.

The activity and selectivity results of Example 5 are shown normalizedto the catalyst from Example 6 in the following Table XI.

TABLE XI Selectivity, normalized Catalyst Activity [DIPB/Cumene (%)]Example 6 99.6 92.1 Example 7 100 100

The catalyst showed both activity and selectivity for the benzenealkylation reaction.

While the illustrative embodiments of this disclosure have beendescribed with particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thisdisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the Examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which this disclosure pertains.

1. A hydrocarbon conversion process, comprising the step of: contactinga hydrocarbon feedstock with a crystalline molecular sieve underconversion conditions to form a conversion product, wherein saidcrystalline molecular sieve has, in its as-synthesized form, an X-raydiffraction pattern including d-spacing maxima at 13.18±0.25 and12.33±0.23 Angstroms, wherein the peak intensity of said d-spacingmaximum at 13.18±0.25 Angstroms is at least as great as 90% of the peakintensity of said d-spacing maximum at 12.33±0.23 Angstroms.
 2. Theprocess of claim 1, wherein said hydrocarbon conversion processcomprises the alkylation of aromatic hydrocarbons, said hydrocarbonfeedstock comprises benzene and long chain olefins comprising a C₁₄olefin, said conversion conditions comprises reaction conditionsincluding, individually or in any combination, a temperature of fromabout 340° C. to about 500° C., a pressure of from about 101 to about20200 kPa-a (absolute), a weight hourly space velocity of from about 2hr⁻¹ to about 2000 hr⁻¹ and an aromatic hydrocarbon/olefin mole ratio offrom about 1/1 to about 20/1, and said conversion product comprises longchain alkyl aromatics.
 3. The process of claim 2, wherein saidhydrocarbon feedstock further comprises toluene, xylene and naphthalene,said reaction conditions includes, a temperature of from about 160° C.to about 260° C. and a pressure of from about 2600 to 3500 kPa-a, andsaid long chain alkyl aromatics are alkylated aromatic lube base stocks.4. The process of claim 2, further comprising the step of sulfonatingsaid long chain alkyl aromatics to provide synthetic detergents.
 5. Theprocess of claim 1, wherein said hydrocarbon conversion processcomprises the alkylation of aromatic hydrocarbons, said hydrocarbonfeedstock comprises benzene and gaseous olefins which comprisespropylene, said conversion conditions comprises reaction conditionsincluding, individually or in any combination, a temperature of fromabout 10° C. to about 125° C., a pressure of from about 101 to about3030 kPa-a, and an aromatic hydrocarbon weight hourly space velocity(WHSV) of from 5 hr⁻¹ to about 50 hr⁻¹, and said conversion productcomprises cumene.
 6. The process of claim 1, wherein said hydrocarbonconversion process comprises the alkylation of reformate, saidhydrocarbon feedstock comprises benzene, toluene and fuel gas, said fuelgas comprising C₅ olefins, said conversion conditions comprisingreaction conditions including, individually or in any combination, atemperature of from about 315° C. to about 455° C., a pressure of fromabout 3000 to about 6000 kPa-a, a WHSV of olefin of from about 0.4 hr⁻¹to about 0.8 hr⁻¹, a WHSV of reformate of from about 1 hr⁻¹ to about 2hr⁻¹ and a gas recycle of from about 1.5 to 2.5 vol/vol fuel gas feed,and said conversion product comprising mono- and di-alkylated aromaticcompounds.
 7. The process of claim 1, wherein said hydrocarbonconversion process comprises the alkylation of aromatic hydrocarbons,said hydrocarbon feedstock comprises benzene and gaseous olefins, saidconversion product comprises alkyl aromatic compounds, said conversionconditions comprises reaction conditions including, individually or inany combination, a temperature of from about 10° C. to about 125° C., apressure of from about 101 to about 3030 kPa-a, and an aromatichydrocarbon weight hourly space velocity (WHSV) of from 5 hr⁻¹ to about50 hr⁻¹.